Treatment of [1,4-(PhS)2C6H4] and [1,2-(PhS)2C6H4] with the appropriate amount of O-mesitylenesulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to give the hydrated free sulfimides [1,4-(PhS{NH2})2C6H4] and [1,2-(PhS{NH2})C6H4PhS]. It would seem that both products display the ability to give two distinct types of material, anhydrous and hydrated forms. The hydrated type [1,4-(PhS{NH2})2C6H4].2H2O has been found by crystallography to form an extended array system; whereas the crystal structure of the dehydrate exhibits extra structural "rigidity" brought about by having two hydrogen-bonded sulfimide units per molecule. The ligand [1,2-(PhS{NH2})C6H4PhS] also exhibits two distinct types of formation, one a dehydrate (exhibited as an oil) and the other a hydrated type (present as a crystalline solid).